Binder resin solution composition, coatings, inks, adhesives and primers

ABSTRACT

The present invention provides a binder resin solution composition, and a coating, ink, and adhesive containing the composition as an active ingredient, the binder resin solution composition having a solid content of 10 to 50 wt. % and comprising (a) a chlorinated polyolefin prepared by chlorinating to a chlorine content of 10 to 40 wt. % an ethylene-propylene-butene ternary random copolymer having an ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8 mol %, and melting point of 129 to 133° C., and (b) an organic solvent.

TECHNICAL FIELD

The present invention relates to a binder resin composition used toprotect or decorate products of polyolefin resins such as polypropylene,polyethylene, ethylene-propylene copolymers, andethylene-propylene-diene copolymers. More particularly, the presentinvention relates to a binder resin solution composition that isexcellent in adhesion to sheets, films, molded articles and the likemade from the aforementioned polyolefin resins and in solventresistance; has excellent low-temperature flowability; and is used forcoatings, primers, printing inks, or adhesives.

BACKGROUND ART

Generally, polyolefin resins are relatively inexpensive and havenoteworthy properties such as chemical resistance, water resistance,heat resistance, etc., and therefore used in a wide variety ofapplications for automotive parts, electronic parts, building materials,food packaging films, and the like. However, since polyolefin resinshaving such remarkable properties are crystalline and non-polar, it isdifficult to coat or bond products made of the resins.

Weakly chlorinated polyolefins exhibiting strong adhesion to polyolefinresins have been used as binder resins to coat or bond such low-adhesionpolyolefin resins. For example, Japanese Examined Patent Publication No.27489/1971 proposes an isotactic polypropylene chlorinated to have achlorine content of 20 to 40 wt. % as a printing ink binder resin forpolypropylene films. Japanese Examined Patent Publication Nos.35445/1975 and 37688/1975 teach propylene-ethylene copolymerschlorinated to 20 to 40 wt. % as binder resins for printing inks andadhesives used on polyolefins.

Moreover, Japanese Examined Patent Publication Nos. 50381/1988 and36624/1988 propose, as primers or binder resins for coating polyolefinmolded articles, weakly chlorinated propylene-α-olefin copolymers with achlorine content of 5 to 50 wt. % containing a carboxylic acid and/orcarboxylic anhydride.

Generally, it is desirable to keep the chlorine content as small aspossible since, as the chlorine content increases, such chlorinatedpolyolefins exhibit reduced solvent resistance and adhesion topolyolefins. However, when the chlorine content is excessively low,properties of the polyolefin solution are impaired, thickening orgelating during storage, thereby resulting in significant deteriorationin coating workability during spray coating and the like. Even when thechlorine content of the chlorinated polyolefins is maintained within arange such that coating workability during spray coating and the likedoes not suffer, the chlorinated polyolefin solutions exhibit impairedflowability when stored at low-temperatures, thereby greatly limitingtheir handling properties at low temperatures such as in winter.Although it is possible to improve low-temperature flowability bykeeping the concentration of the weakly chlorinated polyolefin in thesolution low, when the concentration is excessively low, problems arisesuch as difficult pigment dispersion in solvents upon processing intoinks and coatings, increased transportation cost, etc.

To overcome such problems, Japanese Unexamined Patent Publication No.306227/1994 proposes a binder resin solution, as a binder resin solutioncomposition with excellent low-temperature flowability, that is obtainedby dissolving a weakly chlorinated polyolefin in an alicyclichydrocarbon and aromatic hydrocarbon mixed solvent.

However, the use of such a mixed solvent requires complex process inproduction, resulting in high cost. Moreover, for example, when themixed solvent is used as a part of the primer component for coating,upon blending with a solvent-dispersed resin, its low-temperatureflowability is impaired due to the change in chemical composition of thesolvent. Therefore, it is hardly a fundamental solution to theaforementioned problems.

DISCLOSURE OF THE INVENTION

An object of the invention is to provide a binder resin solutioncomposition for use in coatings, primers, printing inks, or adhesives,without impairing the low-temperature flowability and workability ofweakly chlorinated polyolefins, the composition having excellent solventresistance and outstanding adhesion to polyolefin products.

Other objects and characteristics of the present invention will becomeevident by the disclosure provided hereinbelow.

The inventors conducted extensive research and found that a binder resinsolution composition obtained by dissolving a chlorinated polyolefinprepared by chlorinating an ethylene-propylene-butene ternary randomcopolymer having a specific melting point and composition structure inan organic solvent imparts excellent low-temperature flowability andworkability and exhibits excellent adhesion to polyolefin products andsolvent resistance. The present invention has been accomplished based onthese findings.

In other words, the present invention provides a binder resin solutioncomposition, coating, ink, adhesive, and primer as described below:

-   1. A binder resin solution composition having a solid content of 10    to 50 wt. % comprising (a) a chlorinated polyolefin prepared by    chlorinating to a chlorine content of 10 to 40 wt. % an    ethylene-propylene-butene ternary random copolymer having an    ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8    mol %, and melting point of 129 to 133° C., and (b) an organic    solvent.-   2. A binder resin solution composition having a solid content of 10    to 50 wt. % comprising (a) a carboxyl-containing chlorinated    polyolefin prepared by chlorinating to a chlorine content of 10 to    40 wt. % an ethylene-propylene-butene ternary random copolymer    having an ethylene content of 3.0 to 3.7 mol %, 1-butene content of    2.4 to 2.8 mol %, and melting point of 129 to 133° C. to produce a    chlorinated polyolefin and graft-polymerizing with the chlorinated    polyolefin 1 to 10 wt. % of at least one unsaturated carboxylic acid    monomer selected from the group consisting of carboxylic acids and    carboxylic acid anhydrides, and (b) an organic solvent.-   3. A binder resin solution composition having a solid content of 10    to 50 wt. % comprising (a) a carboxyl-containing chlorinated    polyolefin prepared by graft-polymerizing 1 to 10 wt. % of at least    one unsaturated carboxylic acid monomer selected from the group    consisting of carboxylic acids and carboxylic acid anhydrides with    an ethylene-propylene-butene ternary random copolymer having an    ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8    mol %, and melting point of 129 to 133° C. to produce a    carboxyl-containing polyolefin and chlorinating the    carboxyl-containing polyolefin to a chlorine content of 10 to 40 wt.    %, and (b) an organic solvent.-   4. A coating for a polyolefin film, sheet or molded article, the    coating comprising as an active ingredient the binder resin solution    composition according to any of Items 1 to 3.-   5. An ink for a polyolefin film, sheet or molded article, the ink    comprising as an active ingredient the binder resin solution    composition according to any of Items 1 to 3.-   6. An adhesive for a polyolefin film, sheet or molded article, the    adhesive comprising as an active ingredient the binder resin    solution composition according to any of Items 1 to 3.-   7. A primer for coating a polyolefin resin, the primer comprising as    an active ingredient the binder resin solution composition according    to Item 2 or 3.

Examples of resin components for use in the binder resin solutioncomposition of the present invention include chlorinated polyolefinsprepared by chlorinating ethylene-propylene-butene ternary randomcopolymers; carboxyl-containing chlorinated polyolefins prepared bygraft-polymerizing unsaturated carboxylic acid monomers with chlorinatedpolyolefins prepared by chlorinating ethylene-propylene-butene ternaryrandom copolymers; and carboxyl-containing chlorinated polyolefinsprepared by graft-polymerizing unsaturated carboxylic acid monomers withethylene-propylene-butene ternary random copolymers to givecarboxyl-containing polyolefins and chlorinating the carboxyl-containingpolyolefins.

Examples of ethylene-propylene-butene ternary random copolymers used asstarting materials are polyolefins having an ethylene content of 3.0 to3.7 mol % (preferably 3.1 to 3.6 mol %), 1-butene content of 2.4 to 2.8mol % (preferably 2.5 to 2.7 mol %), propylene content of 93.5 to 94.6mol % (preferably 9.3.7 to 94.4 mol %), and melting point of 129 to 133°C. (preferably 130 to 132° C.). Preferable are those having a molecularweight distribution (Mw/Mn) of 3 to 5.

Ethylene-propylene-butene ternary random copolymers usable herein can beproduced according to a variety of known methods. For example, they canbe produced in the presence of catalysts containing magnesium, titanium,halogen, an electron donor, and aluminum. Examples of such catalystsinclude solid titanium catalytic components containing magnesium,titanium, halogen, and an internal electron donor as an essentialingredient supported by an organic or inorganic carrier; stereoregularcatalysts containing such solid titanium catalytic components, organometallic compounds of metals belonging to Groups 1 to 3 of the periodictable, and external electron donors; and the like.Ethylene-propylene-butene ternary random copolymers usable herein can beproduced by copolymerizing propylene and a small amount of ethylene and1-butene in the presence of such catalysts.

The main component of the catalyst, i.e., a specific solid titaniumcatalytic component, to produce the ethylene-propylene-butene ternaryrandom copolymer is preferably a product of a reaction between titaniumtetrachloride and an alcohol-containing Mg compound conducted in ahydrocarbon solvent.

Examples of polymerization methods include suspension polymerizationconducted in the presence of hydrocarbon solvent or propylene solvent,gas-phase polymerization, and similar methods. Among these methods,suspension polymerization in the presence of propylene solvent andgas-phase polymerization are preferable.

The chlorinated polyolefin used herein has a chlorine content of 10 to40 wt. %. When the chlorine content is lower than 10 wt. %, solubilityin solvents is impaired, and good low-temperature flowability cannot beattained. A chlorine content exceeding 40 wt. % is not preferablebecause adhesion to polyolefins and solvent resistance are compromised.The preferable chlorine content is 20 to 30 wt. %.

The chlorine content of the carboxyl-containing chlorinated polyolefingraft-polymerized with an unsaturated carboxylic acid monomer shouldalso be 10 to 40 wt. %, and preferably 20 to 30 wt. %.

Graft polymerizing an unsaturated carboxylic acid monomer with anethylene-propylene-butene ternary random copolymer can be conductedaccording to known methods, e.g., a polyolefin is brought to reaction byheating it in the presence of radical generator to a temperature aboveits melting point and fusing it (fusion method), or by dissolving apolyolefin in an organic solvent and heating and stirring it in thepresence of radical generator (solution method).

The fusion method provides the advantage of easy operation and quickreaction because a Banbury mixer, kneader, extruder, or like equipmentis used and the reaction is conducted at temperatures higher than themelting point up to 300° C. In the solution method, it is preferable touse toluene, xylene, or a similar aromatic solvent as a reactionsolvent. A reaction temperature of 100 to 180° C. and reaction time of 1to 5 hours causes few side reactions and provides uniform graftpolymers.

Examples of radical generators usable in the reaction includedi-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide,benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate,methyl-ethyl-ketone peroxide, di-tert-butyl peroxide, and likeperoxides; azobisisobutyronitrile, azobisisopropionitrile, and likeazonitriles; etc.

Examples of unsaturated carboxylic acid monomers usable in the reactioninclude maleic acid, maleic anhydride, fumaric acid, citraconic acid,citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride,aconitic acid, aconitic anhydride, himic anhydride, etc.

The grafting ratio of the unsaturated carboxylic acid monomer is 1 to 10wt. %. When it is less than 1 wt. %, sufficient adhesion cannot beattained since the content of polar group in the composition becomesexcessively low. When it is more than 10 wt. %, gelation occurs duringchlorination.

A method for graft-polymerizing an unsaturated carboxylic acid monomerwith a chlorinated polyolefin produced by chlorinating anethylene-propylene-butene ternary random copolymer can be conductedaccording to the solution method described above. The preferablereaction temperature is 60 to 120° C. Excessively low temperatures arenot preferable since the reaction proceeds slowly, and excessively hightemperatures are also not preferable because the chlorinated polyolefindecomposes. The grafting ratio of the unsaturated carboxylic acidmonomer is 1 to 10 wt. %. When the grafting ratio is less than 1 wt. %,the content of polar group in the composition becomes too small,resulting in insufficient adhesion, and a grafting ratio more than 10wt. % results in impaired properties.

Polyolefins can be readily chlorinated according to known methods. Forexample, a polyolefin resin (an ethylene-propylene-butene ternary randomcopolymer, or a carboxyl-containing polyolefin produced by grafting anunsaturated carboxylic acid monomer with such anethylene-propylene-butene ternary random copolymer) is brought toreaction by dissolving in a chlorination solvent, and injecting chlorinegas at a temperature of 50 to 150° C., in the presence of a catalyst orunder UV irradiation, under ambient or increased pressure.

Catalysts usable in the chlorination reaction include, for example,tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, benzoylperoxide, dicumyl peroxide, tert-butylcumyl peroxide, dilauryl peroxide,tert-butyl hydroperoxide, cyclohexanone peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, tert-butyl peroxyisobutylate, andsimilar peroxides; azobisisobutyronitrile, azobisisopropionitrile, andlike azonitriles; etc.

Examples of solvents for use in the chlorinating reaction includehalogenated solvents such as tetrachloroethylene, chloroform and likehalogenated hydrocarbons. Chloroform is especially preferable.

During production of the binder resin solution composition of thepresent invention, the aforementioned chlorinated polyolefins may besolidified, dried, and dissolved in an organic solvent. Alternatively,after the chlorination reaction, the chlorination solvent is removed bydistillation and replaced with the organic solvent.

The solid content of the binder resin solution composition is 10 to 50wt. %. A solid content less than 10 wt. % poses problems such asdifficult pigment dispersion when the solution composition is processedinto inks and coatings, high transportation costs, and other problems. Asolid content more than 50 wt. % is not preferable because the impairedlow-temperature flowability greatly limits handling during winter lowtemperatures. The preferable solid content is 20 to 40 wt. %.

Toluene, xylene, or a similar aromatic organic solvent is preferable asthe organic solvent used in the binder resin solution composition of theinvention.

A feature of the present invention is to further improve properties ofweakly chlorinated polyolefins, which have good adhesion to polyolefins.In particular, although weakly chlorinated polyolefins by nature exhibitbetter adhesion to polyolefins and improved solvent resistance as theirchlorine content is lowered, properties of the solutions thereof aredeteriorated, resulting in thickening/gelation during storage andimpaired low-temperature flowability. Accordingly, coating workabilityduring spray coating and the like is significantly deteriorated andhandling properties during winter low temperatures are greatly impaired.However, a binder resin solution composition, as disclosed herein,comprising as a resin component a weakly-chlorinated polyolefin,obtained by chlorinating an ethylene-propylene-butene ternary randomcopolymer having an ethylene content of 3.0 to 3.7 mol %, a 1-butenecontent of 2.4 to 2.8 mol %, and a melting point of 129 to 133° C., hasexcellent solution quality and low-temperature flowability, as well asexcellent solvent resistance and adhesion to polyolefins.

The binder resin solution composition of the present invention can beused as a binder composition for a coating for polyolefin films, sheets,molded articles, and the like, as well as a binder composition for inks,adhesives, etc. Furthermore, such a composition containing acarboxyl-containing chlorinated polyolefin produced bygraft-polymerizing an unsaturated carboxylic acid monomer can be used asa primer for coating polyolefin bumpers.

Although the binder resin solution composition of the invention can beapplied as a coating per se, it can also be used as a coating or ink bymixing with a pigment, a solvent, or other additives. While the binderresin provides a coating film with well-balanced properties, it canfurther be used in combination with alkyd resins, acrylic resins,polyacryl polyols, polyester resins, polyester polyols, polyetherresins, polyether polyols, polyurethane resins, chlorinated polyolefins,etc., as required.

The binder resin solution composition of the invention, because itachieves excellent solvent resistance and adhesion to polyolefinproducts without impairing the low-temperature flowability andworkability of weakly chlorinated polyolefins, can be used as a binderresin solution composition for coatings, primers, printing inks, oradhesives.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples are given below to illustrate the invention in more detail, butthe scope of the invention is not limited to these examples.

EXAMPLE 1

An ethylene-propylene-butene ternary random copolymer (280 g) having anethylene content of 3.4 mol %, 1-butene content of 2.7 mol %, Mw/Mn of5, and melting point of 131° C. and chloroform (2520 g) were introducedinto an autoclave equipped with a stirrer. After charging it withnitrogen for about 5 minutes, the autoclave was heated to 110° C. tosufficiently fuse the polyolefin resin. Subsequently, 1.4 g oftert-butylperoxy-2-ethylhexanoate was added and chlorine gas wasinjected to acquire 3 reaction solutions each having a differentchlorine content. The reaction solvent, i.e., chloroform, was distilledoff under reduced pressure, and toluene was added to dissolve, therebyproducing toluene solutions of chlorinated polyolefin having a chlorinecontent of 15 wt. %, 20, wt. %, and 25 wt. %, respectively, and a solidcontent of 20 wt. % each.

COMPARATIVE EXAMPLE 1

An isotactic polypropylene having a meso pentad fraction (mmmm) of 0.95and melt flow rate (MFR) of 20 was chlorinated as in Example 1 to obtaintoluene solutions of chlorinated polypropylene having a chlorine contentof 15 wt. %, 20 wt. %, and 25 wt. %, respectively, and a solid contentof 20 wt. % each.

COMPARATIVE EXAMPLE 2

A propylene-ethylene random copolymer having an ethylene content of 3.9mol % and MFR of 12 was chlorinated as in Example 1 to obtain toluenesolutions of chlorinated polyolefin having a chlorine content of 15 wt.%, 20 wt. %, and 25 wt. %, respectively, and a solid content of 20 wt. %each.

COMPARATIVE EXAMPLE 3

A propylene-ethylene-butene random copolymer having an ethylene contentof 4.6 mol %, 1-butene content of 2.2 mol % and MFR of 8 was chlorinatedas in Example 1 to obtain toluene solutions of chlorinated polyolefinhaving a chlorine content of 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

EXAMPLE 2

Graft reaction was conducted over 5 hours by introducing 280 g of anethylene-propylene-butene ternary random copolymer having an ethylenecontent of 3.4 mol %, 1-butene content of 2.7 mol %, Mw/Mn of 5, andmelting point of 131° C.; 16.8 g of maleic anhydride; 5.6 g ofdi-tert-butyl peroxide; and 420 g of toluene into an autoclave equippedwith a stirrer, charging it with nitrogen for about 5 minutes, andheating and stirring at 140° C. After the reaction, the reactionsolution was introduced into an excess of methyl ethyl ketone toprecipitate the resin therefrom. The resin thus obtained was furtherwashed with methyl ethyl ketone several times to remove unreacted maleicanhydride. After drying under reduced pressure, the thus-obtained maleicanhydride-modified polyolefin was chlorinated as in Example 1 to obtaintoluene solutions of maleic anhydride-modified chlorinated polyolefinhaving a chlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

COMPARATIVE EXAMPLE 4

An isotactic polypropylene having a meso pentad fraction (mmmm) of 0.95and MFR of 90 was subjected to reaction according to the methoddescribed in Example 2 to obtain toluene solutions of maleicanhydride-modified chlorinated polypropylene having a chlorine contentof 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %, respectively, and a solidcontent of 20 wt. % each.

COMPARATIVE EXAMPLE 5

A propylene-ethylene random copolymer having an ethylene content of 5.9mol % and MFR of 12 was brought to reaction as in Example 2 to obtaintoluene solutions of maleic anhydride-modified chlorinated polyolefinhaving a chlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

COMPARATIVE EXAMPLE 6

A propylene-ethylene-butene random copolymer having an ethylene contentof 4.6 mol %, 1-butene content of 2.2 mol %, and MFR of 8 was reacted asin Example 2 to obtain toluene solutions of maleic anhydride-modifiedchlorinated polyolefin having a chlorine content of 10 wt. %, 15 wt. %,20 wt. %, and 25 wt. %, respectively, and a solid content of 20 wt. %each.

EXAMPLE 3

An ethylene-propylene-butene ternary random copolymer having an ethylenecontent of 3.4 mol %, 1-butene content of 2.7 mol %, Mw/Mn of 5, andmelting point of 131° C. was chlorinated as in Example 1 to obtaintoluene solutions of chlorinated polyolefin having a chlorine content of10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %, respectively, and a solidcontent of 20 wt. % each. These toluene solutions of chlorinatedpolyolefin (350 g each) were introduced into three-neck flasks equippedwith a stirrer, dropping funnel, thermometer, and refluxer. Maleicanhydride (1 g) was introduced into each flask. After heating thereaction system to 80° C. in an oil bath maintained at a specifictemperature, 0.5 g of benzoyl peroxide diluted with 5 ml of toluene wasadded dropwise via the dropping funnel over a period of about 10minutes. After dropwise addition, reaction was carried out for 5 hoursby stirring while maintaining the reaction system at 80° C. Afterreaction, the reaction solutions were cooled and treated with a smallamount of toluene, thereby yielding toluene solutions of maleicanhydride-modified chlorinated polyolefin each having a solid content of20 wt. %.

Chlorinated polyolefin solutions obtained in Examples 1 to 3 andComparative Examples 1 to 6 were investigated for the followingproperties:

(1) Low-Temperature Flowability

Tables 1 and 2 show a property (low-temperature flowability) of thechlorinated polyolefin solutions obtained in Examples 1 to 3 andComparative Examples 1 to 6 after storing each chlorinated polyolefinsolution for 10 days in the air at 5° C., −5° C., or −10° C., wherein Ameans “flowable” and B refers to “not flowable (gelated)”.

(2) Gasoline Resistance

The viscosity of the chlorinated polyolefin solutions obtained inExamples 1 to 3 and Comparative Examples 1 to 6 was adjusted by tolueneso that the drain time using a Ford cup #4 was 12 sec/20° C. Thesesolutions were spray-coated onto polypropylene boards (produced bypress-molding SB-E3 manufactured by Mitsui Chemicals, Inc., according toknown method; 100 mm×50 mm; thickness: 2 mm) washed with isopropylalcohol, and dried at 80° C. for 10 minutes. A two-component urethanecoating was further spray-coated thereon in an amount of 50 to 60 g/m²,and the boards were dried for about 10 minutes at room temperature andfor 45 minutes at 80° C. Testing was conducted on the polypropyleneboards after being left for 24 hours at room temperature. The coatedpolypropylene boards were scratched through to the underlying boardsurface, and immersed for 2 hours in conventional unleaded gasolinemaintained at 20° C., after which the condition of the coatings wasexamined. Results are shown in Tables 1 and 2.

(3) Interlaminar Adhesion

Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples2 and 3 and Comparative Examples 4 to 6 were provided with a gridpattern of hundred 1-mm squares that reach the underlying board surface.An adhesive cellophane tape was placed on the grid, the tape was peeledperpendicular to the coated surface, and the number of squares that werenot peeled away with the tape was counted. Table 2 shows the results.

(4) Interlaminar Adhesion After Immersion in Warm Water

Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples2 and 3 and Comparative Examples 4 to 6 were immersed in warm watermaintained at 40° C. for 240 hours and subjected to the same examinationas in (3) above. Table 2 shows the results.

(5) Gasohol Resistance

Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples2 and 3 and Comparative Examples 4 to 6 were immersed in gasohol(conventional unleaded gasoline: ethanol=90:10 (weight ratio))maintained at 20° C. for 120 minutes, and the condition of the coatingswas examined. Table 2 shows the results.

TABLE 1 Low-temperature Chlorine flowability Gasoline content (Wt. %) 5°C. −5° C. −10° C. resistance Example 1 15 A B B No peeling 20 A A B Nopeeling 25 A A A No peeling Comparative 15 B B B No peeling Example 1 20B B B No peeling 25 A B B Peeling Comparative 15 B B B No peelingExample 2 20 A B B No peeling 25 A A B Peeling Comparative 15 B B B Nopeeling Example 3 20 A B B No peeling 25 A A B PeelingAnalysis of the Results Provided in Table 1

In Example 1, an ethylene-propylene-butene ternary random copolymerhaving an ethylene content of 3.4 mol %, 1-butene content of 2.7 mol %,Mw/Mn of 5, and melting point of 131° C. was chlorinated and dissolvedin an organic solvent. In Comparative Examples 1, 2 and 3, chlorinatedpolyolefins were dissolved in an organic solvent. The solution ofExample 1 is clearly superior to those of Comparative Examples 1, 2 and3 in low-temperature flowability. Moreover, the polymer of Example 1 isalso superior in gasoline resistance.

TABLE 2 Interlaminar Chlorine Low-temperature adhesion after contentflowability Interlaminar immersion in Gasoline Gasohol (Wt. %) 5° C. −5°C. −10° C. adhesion warm water resistance resistance Ex. 2 10 A B B 100100 No peeling No peeling 15 A B B 100 100 No peeling No peeling 20 A AA 100 100 No peeling No peeling 25 A A A 90 90 No peeling No peeling Ex.3 10 A B B 100 100 No peeling No peeling 15 A B B 100 100 No peeling Nopeeling 20 A A A 100 100 No peeling No peeling 25 A A A 90 90 No peelingNo peeling Comp. 10 B B B 100 100 No peeling No peeling Ex. 4 15 B B B80 80 No peeling No peeling 20 B B B 75 75 No peeling No peeling 25 A AB 50 60 Peeling Peeling Comp. 10 B B B 100 100 No peeling No peeling Ex.5 15 B B B 100 100 No peeling No peeling 20 A B B 100 100 No peeling Nopeeling 25 A A A 75 75 Peeling Peeling Comp. 10 B B B 100 100 No peelingNo peeling Ex. 6 15 B B B 100 100 No peeling No peeling 20 A B B 100 100No peeling No peeling 25 A A A 75 70 Peeling PeelingAnalysis of the Results Provided in Table 2

In Example 2, an ethylene-propylene-butene ternary random copolymerhaving an ethylene content of 3.4 mol %, 1-butene content of 2.7 mol %,Mw/Mn of 5, and melting point of 131° C. was modified by maleicanhydride and then chlorinated, followed by being dissolved in anorganic solvent. In Example 3, an ethylene-propylene-butene ternaryrandom copolymer as used in Example 2 was chlorinated and then modifiedby maleic anhydride, followed by being dissolved in an organic solvent.In Comparative Examples 4, 5 and 6, polyolefins graft-modified withmaleic anhydride were chlorinated and dissolved in an organic solvent.In spite of their better low-temperature flowability, the polymers usedin Examples 2 and 3 are also superior to those used in ComparativeExamples 4, 5 and 6 in coating film property. Therefore, the polymers ofExamples 2 and 3 can be considered as unprecedented polymers combiningoutstanding low-temperature flowability and excellent coating filmproperties.

1. A binder resin solution composition having a solid content of 10 to 50 wt. % comprising (a) a chlorinated polyolefin prepared by chlorinating to a chlorine content of 25 to 30 wt. % an ethylene-propylene-butene ternary random copolymer having an ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8 mol %, and melting point of 129 to 133° C., and (b) an organic solvent.
 2. A binder resin solution composition having a solid content of 10 to 50 wt. % comprising (a) a carboxyl-containing chlorinated polyolefin prepared by chlorinating to a chlorine content of 20 to 30 wt. % an ethylene-propylene-butene ternary random copolymer having an ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8 mol %, and melting point of 129 to 133° C. to produce a chlorinated polyolefin and graft-polymerizing with the chlorinated polyolefin 1 to 10 wt. % of at least one unsaturated carboxylic acid monomer selected from the group consisting of carboxylic acids and carboxylic acid anhydrides, and (b) an organic solvent.
 3. A binder resin solution composition having a solid content of 10 to 50 wt. % comprising (a) a carboxyl-containing chlorinated polyolefin prepared by graft-polymerizing 1 to 10 wt. % of at least one unsaturated carboxylic acid monomer selected from the group consisting of carboxylic acids and carboxylic acid anhydrides with an ethylene-propylene-butene ternary random copolymer having an ethylene content of 3.0 to 3.7 mol %, 1-butene content of 2.4 to 2.8 mol %, and melting point of 129 to 133° C. to produce a carboxyl-containing polyolef in and chlorinating the carboxyl containing polyolefin to a chlorine content of 20 to 30 wt. %, and (b) an organic solvent.
 4. A coating for a polyolefin film, sheet or molded article, the coating comprising as an active ingredient the binder resin solution composition according to claim
 1. 5. A coating for a polyolefin film, sheet or molded article, the coating comprising as an active ingredient the binder resin solution composition according to claim
 2. 6. A coating for a polyolefin film, sheet or molded article, the coating comprising as an active ingredient the binder resin solution composition according to claim
 3. 7. An ink for a polyolefin film, sheet or molded article, the ink comprising as an active ingredient the binder resin solution composition according to claim
 1. 8. An ink for a polyolefin film, sheet or molded article, the ink comprising as an active ingredient the binder resin solution composition according to claim
 2. 9. An ink for a polyolef in film, sheet or molded article, the ink comprising as an active ingredient the binder resin solution composition according to claim
 3. 10. An adhesive for a polyolefin film, sheet or molded article, the adhesive comprising as an active ingredient the binder resin solution composition according to claim
 1. 11. An adhesive for a polyolefin film, sheet or molded article, the adhesive comprising as an active ingredient the binder resin solution composition according to claim
 2. 12. An adhesive for a polyolefin film, sheet or molded article, the adhesive comprising as an active ingredient the binder resin solution composition according to claim
 3. 13. A primer for coating a polyolefin resin, the primer comprising as an active ingredient the binder resin solution composition according to claim
 2. 14. A primer for coating a polyolefin resin, the primer comprising as an active ingredient the binder resin solution composition according to claim
 3. 